JP2014094491A - Laminate and tire - Google Patents

Laminate and tire Download PDF

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JP2014094491A
JP2014094491A JP2012246668A JP2012246668A JP2014094491A JP 2014094491 A JP2014094491 A JP 2014094491A JP 2012246668 A JP2012246668 A JP 2012246668A JP 2012246668 A JP2012246668 A JP 2012246668A JP 2014094491 A JP2014094491 A JP 2014094491A
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rubber
acrylate
layer
mass
tire
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JP5947701B2 (en
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Takahiro Miura
貴裕 三浦
Daisuke Nakagawa
大助 中川
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Bridgestone Corp
株式会社ブリヂストン
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Abstract

PROBLEM TO BE SOLVED: To provide a laminate excellent in adhesion property between a coloring layer and a lower rubber arranged under the coloring layer and aging durability, and to provide a tire using the laminate.SOLUTION: A laminate contains a coloring layer 12 obtained by curing an energy ray-curable coating, and a lower layer rubber 11 arranged under the coloring layer 12 and obtained by using a rubber composition in which 0.8 to 30 pts.mass of an acrylate compound is blended based on 100 pts.mass of a rubber component.

Description

  The present invention relates to a laminate comprising a colored layer and a rubber layer provided in contact with the colored layer, and a tire using the laminate.

  Conventionally, also in rubber products such as tires, as with other molded products, coloring processing such as painting and printing on the surface has been widely performed for the purpose of decorating and improving visibility. In addition, a tire is disclosed in which a colored layer made of a polyurethane layer is provided on a sidewall in order to ensure desired decoration and visibility while suppressing deterioration of the colored layer.

JP-T-2004-526814

  However, when the colored layer disclosed in Patent Document 1 is applied to a rubber member of a tire, the adhesion between the colored layer and the lower layer rubber is low. There was a problem that peeling and cracking occurred.

  Therefore, the present invention provides a laminate having excellent adhesion and decoration durability between a colored layer and a lower rubber disposed under the colored layer, and a tire using the laminate. The purpose is to do.

The gist of the present invention is as follows.
(1) The laminate of the present invention is a colored layer obtained by curing an energy ray curable paint, and is disposed under the colored layer, and the acrylate compound is added in an amount of 0.8 to 30 parts by mass with respect to 100 parts by mass of the rubber component. And a lower rubber formed by applying the blended rubber composition.
(2) Moreover, it is preferable that the said acrylate compound consists of an acrylate oligomer and / or an acrylate monomer.
(3) In addition, it is preferable that content of the anti-aging agent of the said rubber composition is 3 mass parts or less with respect to 100 mass parts of rubber components.
(4) Moreover, it is preferable that the said energy ray is an ultraviolet-ray.
(5) It is preferable that a white ink layer is further provided as a lower layer of the colored layer.
(6) The tire according to the present invention is characterized in that the above-described laminate is used for a sidewall portion.

  According to the present invention, in addition to ensuring desired decoration and visibility, a laminate including a colored layer excellent in adhesion to the lower rubber and decoration durability, and a tire using the laminate Can be provided.

It is sectional drawing which showed typically the one part about one Embodiment of the rubber laminated body of this invention. 1 is a cross-sectional view in the width direction schematically showing a part of an embodiment of a tire of the present invention.

Hereinafter, the configuration and reason for limitation of the present invention will be described with reference to the drawings.
As shown in FIG. 1, the laminate according to the present invention includes a colored layer 13 and a colored layer 12 provided in contact with the colored layer. Hereinafter, each member will be described.

(Colored layer)
The colored layer constituting the laminate of the present invention is formed by curing an energy ray curable paint.
By using the energy ray-curable coating material, it is possible to improve the adhesion between the colored layer and the lower rubber disposed under the colored layer while ensuring desired decoration and visibility, and the energy ray. The curable paint can significantly reduce the curing time of the coating film compared to the thermosetting and solvent volatile type paints, and it can prevent the lower layer rubber from deteriorating because it does not generate heat when the coating film is cured. There is an effect.

The colored layer contains a colorant in order to achieve desired decoration and visibility. The colorant is blended so that the color layer has a color different from that of the lower layer rubber. For example, when the lower layer rubber is black, a colorant other than black is used.
Here, an organic or inorganic pigment or dye can be used as the colorant. For example, titanium oxide etc. are mentioned as an inorganic pigment. For example, white colorants include titanium oxide, antimony white, zinc sulfide and the like, and red colorants include bengara, cadmium red, red lead, mercury sulfide, cadmium, permanent red 4R, risor red, pyrazolone red, Watching Red, Calcium Salt, Lake Red D, Brilliant Carmine 6B, Eosin Lake, Rhodamine Lake B, Alizarin Lake, Brilliant Carmine 3B, C.I. I. Pigment red 2 and the like, and examples of the blue colorant include C.I. I. Pigment blue 15: 3, C.I. I. Pigment Blue 15, Bituminous Blue, Cobalt Blue, Alkaline Blue Lake, Victoria Blue Lake, Phthalocyanine Blue, Metal-free Phthalocyanine Blue, Partially Chlorinated Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue BC, etc. , Yellow lead, zinc yellow, cadmium yellow, yellow iron oxide, mineral first yellow, nickel titanium yellow, navel yellow, naphthol yellow S, hansa yellow G, hansa yellow 10G, benzidine yellow G, benzidine yellow GR, quinoline yellow lake, permanent Yellow NCG, Tartrazine Lake, C.I. I. Pigment yellow 12 and the like. In addition, the usage-amount of a coloring agent has the preferable range of 1-50 mass% of the total amount of an oligomer and a monomer.

  The energy ray curable coating material is a coating material that is cured by irradiation with energy rays, preferably ultraviolet rays or infrared rays, more preferably ultraviolet rays. Specifically, a photopolymerization initiator, an oligomer, a monomer, and the colorant are main components, and further, an ultraviolet absorber, an antioxidant, a light stabilizer, an adhesion promoter, a rheology modifier, and a dispersant as necessary. Etc. are blended. The energy ray curable coating material can also be diluted with a solvent to adjust the viscosity.

  As the photopolymerization initiator, for example, a radical photopolymerization initiator is used. Here, more specifically, the radical photopolymerization initiator is benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenyl sulfide, isopropylthioxanthone, diethylthioxanthone, methyl 4- (diethylamino) benzoate. Hydrogen abstraction type initiator such as benzoin ether, benzoylpropyl ether, benzyl dimethyl ketal and other intramolecular cleavage type initiators; 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone , Α-hydroxyalkylphenone type initiators such as alkylphenylglyoxylate and diethoxyacetophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2- Zimechi Amino-1- (4-morpholinophenyl) alpha-aminoalkylphenone type initiators such as butanone -1; acylphosphine oxide and the like. These radical photopolymerization initiators may be used alone or in combination of two or more. In addition, the usage-amount of radical photopolymerization initiator has the preferable range of 0.1-10.0 mass% of the total amount of the oligomer and monomer mentioned later.

  Moreover, a photocationic polymerization initiator can also be used as the photopolymerization initiator. Here, more specifically, the photocationic polymerization initiator may include (4-methylphenyl) [4- (2-methylpropyl) phenyl] iodonium hexafluorophosphate (IRGACURE 250). . These photocationic polymerization initiators may be used alone or in combination of two or more. In addition, the usage-amount of a photocationic polymerization initiator has the preferable range of 0.1-10.0 mass% of the total amount of the oligomer and monomer mentioned later.

  As the monomer used for the radical photopolymerization, an acrylate monomer and a methacrylate monomer are preferable. Here, the acrylate monomer and the methacrylate monomer play a role of improving adhesion to rubber and controlling the elastic modulus, and are also necessary for adjusting the viscosity of the coating solution of the ultraviolet curable coating material. The blending amount is determined by appropriately adjusting depending on the oligomer used. Specific examples of the monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-ethylhexyl polyethoxy (meth) acrylate, and benzyl (meth) acrylate. , Isobornyl (meth) acrylate, phenoxyethyl (meth) acrylate, tricyclodecane mono (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, morpholine acrylate (acryloylmorpholine), N- Vinyl caprolactam, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, o-phenylphenyloxyethyl (meth) acrylate, isobonyl (meth) acrylate Monofunctional monomers such as rate; neopentyl glycol di (meth) acrylate, neopentyl glycol dipropoxy di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate Bifunctional monomers such as 1,6-hexanediol di (meth) acrylate and nonanediol di (meth) acrylate; trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) Multifunctional monomers such as acrylate, dipentaerythritol hexaacrylate, tris [(meth) acryloxyethyl] isocyanurate, ditrimethylolpropane tetra (meth) acrylate It can be mentioned. The monomer content in the energy ray curable coating is preferably in the range of 10 to 80% by mass.

  The oligomer used for the radical photopolymerization has a reactive functional group in addition to a reactive oligomer such as urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, and (meth) acrylate of an acrylic resin. Compounds that are not present can also be used as appropriate. Here, “(meth) acrylate” includes both acrylate and methacrylate. The oligomer content in the ultraviolet curable coating is preferably in the range of 20 to 80% by mass.

  The monomer used for the cationic photopolymerization is preferably an epoxy acrylate or methacrylate. Here, the epoxy-based acrylate or methacrylate plays a role of improving adhesion to rubber and controlling the elastic modulus, and is also necessary for adjusting the viscosity of the coating solution of the ultraviolet curable paint. The blending amount is determined by appropriately adjusting depending on the oligomer used. Specific examples of the monomer include 2-hydroxy-3-phenoxypropyl acrylate. The content of the monomer in the ultraviolet curable coating is preferably in the range of 10 to 80% by mass.

  As the oligomer used for the cationic photopolymerization, a commercially available oligomer capable of cationic photopolymerization can be used, and specifically, an epoxy acrylate oligomer can be used. In addition, it is preferable that content of the said oligomer in an ultraviolet curable coating material is the range of 20-80 mass%.

  Furthermore, the other compounding agents blended in the energy beam curable coating material are appropriately blended for improving weather resistance, heat resistance, etc., adjusting the viscosity, and the like.

In addition, it does not specifically limit about the method of forming the said colored layer using the said energy-beam curable coating material.
For example, the energy ray curable coating is applied on the vulcanized lower rubber surface by a method such as screen printing, ink jet printing, letterpress printing, or tampon printing, and then the application layer is irradiated with energy rays and cured. Thus, a colored layer can be formed on the outer surface of the lower rubber layer. In addition, a rubber material is obtained by in-mold molding in which a film obtained by applying an energy ray curable coating material on a release film in advance and irradiating and curing the energy ray is inserted when vulcanizing rubber materials such as tires. A colored layer may be provided on the surface.

  Further, the thickness of the colored layer is not particularly limited, but is preferably in the range of 5 to 100 μm. If the thickness is less than 5 μm, the designability may not be sufficiently secured, while if it exceeds 100 μm, the production cost increases.

  Furthermore, it is preferable that a white ink layer is further provided as a lower layer of the colored layer. By providing the white ink layer, it is possible to conceal the black color of the lower rubber, and if the color layer is formed thereon, the design can be further improved. The thickness of the white layer is preferably about 10 to 40 μm although it depends on the amount of white pigment to be blended.

(Lower rubber)
As shown in FIG. 1, the laminate of the present invention comprises a lower layer rubber 11 under the colored layer 12, and the lower layer rubber is characterized by applying a rubber composition containing an acrylate compound. The acrylate compound blended in the rubber composition constituting the lower rubber 11 reacts with the energy curable paint constituting the colored layer 12 and cures together, whereby the lower rubber 11 and the colored layer 12 are cured. Adhesiveness and decoration durability can be greatly improved. The mechanism by which the acrylate compound is cured is shown below.

  Furthermore, when the acrylate compound is blended in the rubber composition, the acrylate compound has a relatively low molecular weight, and therefore, after the vulcanization of the lower layer rubber, it tends to move to the surface and be unevenly distributed near the surface. Therefore, there is also an advantage that high adhesion with the colored layer can be secured even with a small addition amount.

  Here, the acrylate compound is not particularly limited as long as it reacts with the energy ray curable coating material, and includes, for example, an acrylate oligomer and / or an acrylate monomer.

  Here, examples of the acrylate monomer include the same monomers as those in the case of the energy ray curable paint described above. The acrylate oligomer is a polymer of the acrylate monomer described above, and the degree of polymerization is about 2 to 500.

  Furthermore, the compounding quantity of the said acrylate oligomer needs to be 0.8-30 mass parts with respect to 100 mass parts of said rubber components, and it is preferable to set it as 0.8-25 mass parts. When the blending amount is less than 0.8 parts by mass, the content of the acrylate oligomer is not sufficient, so that the adhesion with the colored layer is reduced, whereas when the blending amount exceeds 30 parts by mass, the rubber physical properties are reduced, This is because workability at the time of unvulcanization is lowered.

  Moreover, natural rubber (NR) and synthetic rubber can be used as a rubber component contained in the rubber composition constituting the lower rubber. Here, synthetic rubbers such as synthetic polyisoprene rubber (IR), styrene-butadiene copolymer rubber (SBR), polybutadiene rubber (BR), butyl rubber (IIR), halogenated butyl rubber [brominated butyl rubber] Non-diene rubbers such as (Br-IIR), chlorinated butyl rubber (Cl-IIR) and the like] and ethylene-propylene-diene rubber (EPDM). These rubber components may be used alone or in combination of two or more. In the present invention, the non-diene rubber means a rubber in which the proportion of units derived from a diene monomer in the monomer units constituting the non-diene rubber is 5 mol% or less. Here, examples of the diene monomer include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, and the like. On the other hand, examples of non-diene-based (non-diene-based) monomers constituting the non-diene rubber include ethylene, propylene, and isobutene.

  Further, the rubber composition constituting the lower layer rubber, the content of the anti-aging agent is preferably 3 parts by mass or less, more preferably 1.5 parts by mass or less, relative to 100 parts by mass of the rubber component. The amount is preferably less than 1.0 part by mass. In the rubber composition applied to the lower layer rubber, when the content of the anti-aging agent exceeds 1.5 parts by mass with respect to 100 parts by mass of the rubber component, the migration of the anti-aging agent to the surface layer (bloom) increases, Curing of the energy ray curable coating may be inhibited, and the adhesion between the colored layer and the lower layer rubber may be reduced. On the other hand, in the rubber composition to be applied to the lower layer rubber, the content of the anti-aging agent is less than 1.0 part by mass with respect to 100 parts by mass of the rubber component, so that the curing of the energy ray curable paint becomes particularly good and coloring The adhesion between the layer and the lower layer rubber can be further improved.

  Examples of the antiaging agent include N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine (6PPD), 2,2,4-trimethyl-1,2-dihydroquinoline polymer ( TMDQ), 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline (AW), N, N′-diphenyl-p-phenylenediamine (DPPD), N, N′-di-sec-butyl -P-phenylenediamine, N-phenyl-N '-(methylheptyl) -p-phenylenediamine and the like.

  The rubber composition applied to the lower layer rubber includes, in addition to the rubber component and anti-aging agent described above, a filler such as carbon black, a vulcanizing agent such as sulfur, a vulcanization accelerator, a process oil, and a scorch inhibiting agent. The compounding agents usually used in the rubber industry such as zinc white and stearic acid can be appropriately selected and blended within a range not impairing the object of the present invention. As these compounding agents, commercially available products can be suitably used. The rubber composition applied to the lower rubber layer can be produced by kneading the rubber component with various compounding agents appropriately selected as necessary, heating, extruding, and the like.

(Protective layer)
As shown in FIG. 1, the rubber laminate of the present invention preferably further includes a protective layer 13 on the colored layer 12. The protective layer 13 has its elasticity, impact resistance, wear resistance, and the like, and is a layer for protecting the colored layer 12.

  Moreover, as the protective layer, various protective layers made of an inorganic hard material are generally known for those that do not deform. For example, considering that the rubber laminate of the present invention is used for a sidewall portion of a pneumatic tire to protect against external friction and impact, the protective layer may be damaged by such friction or impact. It is preferable that the protective layer is made of a hard material that does not generate water, and a protective layer made of an aqueous urethane resin is particularly preferable. By using such a water-based urethane resin as the protective layer, a protective layer that is elastic and can withstand repeated strain accompanying tire deformation, and has excellent impact resistance, wear resistance, contamination resistance, and water resistance can be obtained. It is done. Accordingly, it is possible to prevent the rubber or the paint layer inside the protective layer 13 from being scratched or peeled off when traveling on a rough road or during a car wash, and therefore the rubber formed on the rubber or the rubber surface of the tire sidewall. It is possible to maintain the aesthetics of the decoration.

  As an example of the water-based urethane resin, a hydroxyl group-containing polyester obtained by reacting a polyol component and a polybasic component, and a polyisocyanate are contained, and at least the polyol component of the polyol component and the polybasic component is the component. There is an aqueous urethane resin (urethane resin example 1) having an alicyclic structure in the molecule, and for example, an aqueous urethane resin described in JP-A-10-234848 and JP-A-2001-271027 is applied. be able to.

  The thickness of the protective layer is preferably in the range of 5 to 40 μm. If it is less than this range, the effect of protecting the tire as a protective layer is not sufficient, and if it exceeds this range, it is disadvantageous in that it cannot withstand repeated strain accompanying tire deformation and breaks as a protective layer. A more preferable range is a range of 10 to 30 μm.

In addition, when the rubber layered body of the present invention is used as a tire member, the protective layer contains an ultraviolet absorber, so that discoloration and aging of rubber and a colored film can be suppressed and weather resistance can be improved. Therefore, it is preferable. As a result, there is an effect that the content of the anti-aging agent can be reduced.
As the ultraviolet absorber, for example, a commercially available ultraviolet absorber such as a benzophenone ultraviolet absorber, a benzotriazole ultraviolet absorber, a triazine ultraviolet absorber, or a cyanoacrylate ultraviolet absorber can be used.

  Moreover, it is preferable to set it as the range of 0.5-4.0 mass parts with respect to 100 mass parts of curable urethane coatings as a compounding quantity of a ultraviolet absorber. Further, as described above, the curable urethane coating may contain a pigment, a fluorescent brightening agent, a curing catalyst, a leveling agent and the like in addition to the ultraviolet absorber.

(tire)
The tire according to the present invention is characterized in that the above-described laminate of the present invention is used for a sidewall portion.
For example, as shown in FIG. 2, the tire includes a pair of bead portions 1, a pair of sidewall portions, a tread portion 3 connected to both sidewall portions, and a bead core 4 embedded in each bead portion 1. A torus-like carcass 5 and a belt 6 disposed on the outer side in the tire radial direction of the crown portion of the carcass 5, and a colored layer 7 on a part of the tire outer surface of the sidewall portion 2, A lower layer rubber 8 is provided adjacent to the inner surface of the colored layer 7 (in the illustrated example, the inner side in the tire width direction), and a protective layer 9 is provided on the outer surface of the tire.

  The carcass 5 in the illustrated example is composed of a single carcass ply, and has a main body portion extending in a toroidal shape between the pair of bead cores 4 and around each bead core 4 from the inside to the outside in the tire width direction. In the tire of the present invention, the number of plies and the structure of the carcass 5 are not limited to this. Further, in the illustrated tire, a belt 6 composed of two belt layers is disposed on the outer side in the tire radial direction of the crown portion of the carcass 5, and the belt layer is usually inclined with respect to the tire equatorial plane. The two belt layers are laminated such that the steel cords constituting the belt layers intersect with each other across the tire equatorial plane to constitute the belt 6. The belt 6 in the figure is composed of two belt layers, but in the tire of the present invention, the number of belt layers constituting the belt 6 may be three or more. Moreover, although the tire shown in FIG. 2 is a tire for passenger cars, the tire of this invention is not limited to this.

  In addition, the tire shown in FIG. 2 includes a colored layer 7 on the outer surface of the tire side portion 2 and a lower rubber 8 below (inner tire side) in the maximum width portion of the tire. The tire is not limited to this, and for example, the entire rubber disposed on the outer side in the tire width direction of the carcass 5 of the tire side portion 2 is the lower layer rubber 8, and the colored layer 7 is disposed thereon. Tires and the like are also one preferred embodiment of the present invention.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these.

(Examples 1-4 and Comparative Examples 1-5)
(1) Production of rubber composition The raw materials shown in Table 1 were mixed by a Banbury mixer to prepare a rubber composition. Thereafter, the resulting rubber composition was vulcanized at 160 ° C. for 13 minutes to produce a lower layer rubber.

(2) Production of Laminate Next, on the surface of the obtained lower rubber, polycaprolactam skeleton urethane acrylate oligomer (16 mass%), polyester skeleton urethane acrylate oligomer (21 mass%), phenoxyethyl acrylate (21 mass%) ), Dicyclopentanyl acrylate (26% by mass), photopolymerization initiator (IRGACURE 127) (3% by mass), and photopolymerization initiator (IRGACURE 652) (3% by mass), The film was applied by an ink jet method so that the film thickness was 10 μm.
Then, using SUBZERO 085 (UV lamp system, manufactured by Integration Co., Ltd., output: 100 W / cm), the ink composition (ultraviolet curable paint) was cured under the conditions of 800 mW / cm 2 and 60 seconds. The measurement of the integrated light quantity and peak illuminance was performed using an ultraviolet light quantity meter Power Pack (manufactured by EIT). Thereby, the sample of the laminated body provided with a colored layer and a laminated rubber was produced.

(Evaluation)
(1) Adhesiveness of colored layer Samples of each laminate were allowed to stand in a thermostatic bath at 60 ° C for 48 hours, and then a cross-cut adhesion test was performed on the colored layer in accordance with JIS K5600-5-6. The adhesion of the colored layer was evaluated. The reciprocal of the number of grids from which the colored layer of the tire of Comparative Example 4 was peeled was 40, and the index was displayed. The higher the index value, the higher the adhesion between the colored layer and the lower layer rubber and the decoration durability. The evaluation results are shown in Table 1. In addition, about the sample in which the colored layer did not harden | cure but the adhesive evaluation of a colored layer and lower layer rubber | gum was not able to be performed, it displayed as (uncured).

(2) Fracture resistance After each laminate was molded to a thickness of 2 mm, a tensile test in accordance with JIS # 3 was performed, and the fracture strength was evaluated by measuring the fracture strength of each sample. .
About evaluation, it displays as an index value when Example 1 is set to 100, and the larger the numerical value, the greater the breaking strength and the better the fracture resistance. The evaluation results are shown in Table 1.

* 1: RSS # 1
* 2: Carbon black, FEF, iodine adsorption amount = 43 g / kg, DBP oil absorption amount = 121 ml / 100 g, N 2 SA (nitrogen adsorption specific surface area) = 42 m 2 / g, “Asahi # 65” manufactured by Asahi Carbon Co., Ltd.
* 3: MXST made by Miyoshi Oil
* 4: N- (1,3-dimethylbutyl) -N′-p-phenylenediamine, knock rack 6C manufactured by Ouchi Shinsei Chemical Co., Ltd.
* 5: “Hakusuitec” manufactured by Kyushu Hakusui
* 6: N-cyclohexyl-2-benzothiazolylsulfenamide, Noxeller CZ-G manufactured by Ouchi Shinsei Chemical Co., Ltd.
* 7: Shikoku Kasei Kogyo Co., Ltd. Mukuron OT-20
* 8: Pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer (manufactured by Daicel Cytec)
* 9: Hydroxypivalate neopentyl glycol acrylic acid adduct (manufactured by Kyoeisha Chemical Co., Ltd.)
* 10: 2-hydroxypropyl ethyl ester (manufactured by Kyoeisha Chemical Co., Ltd.)

  From the results of Table 1, it was found that all the laminates according to the examples of the present invention were excellent in the adhesion and the fracture resistance of the colored layer. On the other hand, the comparative example was found to be inferior in performance as compared to the example.

  ADVANTAGE OF THE INVENTION According to this invention, the laminated body excellent in the adhesiveness of a colored layer and lower-layer rubber arrange | positioned under this colored layer and decoration durability can be provided. As a result, when the laminate is used for a tire, the tire can be used for a longer period of time, and an industrially useful effect is achieved.

DESCRIPTION OF SYMBOLS 1 Bead part 2 Tire side part 3 Tread part 4 Bead core 5 Carcass 6 Belt 7 Colored layer 8 Lower layer rubber 9 Protective layer 10 Laminated body 11 Lower layer rubber 12 Colored layer 13 Protective layer

Claims (6)

  1. A colored layer formed by curing an energy ray curable coating;
    A lower rubber formed by applying a rubber composition disposed under the colored layer and blended with 0.8 to 30 parts by mass of an acrylate compound with respect to 100 parts by mass of a rubber component;
    A laminate comprising:
  2.   The laminate according to claim 1, wherein the acrylate compound includes an acrylate oligomer and / or an acrylate monomer.
  3.   The laminate according to claim 1, wherein the content of the antioxidant in the rubber composition is 3 parts by mass or less with respect to 100 parts by mass of the rubber component.
  4.   The laminate according to claim 1, wherein the energy ray is ultraviolet rays.
  5.   The laminate according to claim 1, further comprising a white ink layer as a lower layer of the colored layer.
  6. A tire comprising the laminate according to any one of claims 1 to 5 as a sidewall portion.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60259434A (en) * 1984-06-05 1985-12-21 Sony Corp Coloring method of automobile tire
JPH11124471A (en) * 1997-10-23 1999-05-11 Yokohama Rubber Co Ltd:The Pneumatic tire
JP2003082308A (en) * 2001-06-29 2003-03-19 Toppan Forms Co Ltd Pressure-sensitive adhesive composition and sheet for information carrier using the same
JP2003170539A (en) * 2001-12-10 2003-06-17 Dainippon Printing Co Ltd Decorative paper
JP2010125440A (en) * 2008-12-01 2010-06-10 Bridgestone Corp Inkjet printing apparatus for doughnut type (ring type) article

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60259434A (en) * 1984-06-05 1985-12-21 Sony Corp Coloring method of automobile tire
JPH11124471A (en) * 1997-10-23 1999-05-11 Yokohama Rubber Co Ltd:The Pneumatic tire
JP2003082308A (en) * 2001-06-29 2003-03-19 Toppan Forms Co Ltd Pressure-sensitive adhesive composition and sheet for information carrier using the same
JP2003170539A (en) * 2001-12-10 2003-06-17 Dainippon Printing Co Ltd Decorative paper
JP2010125440A (en) * 2008-12-01 2010-06-10 Bridgestone Corp Inkjet printing apparatus for doughnut type (ring type) article

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